The AlNbTiZr medium-entropy alloy (MEA) coatings with different Al contents were prepared on N36 zirconium alloy substrates by RF magnetron co-sputtering. The morphology, microstructure, mechanical properties, surface wettability and corrosion resistance of the AlNbTiZr MEA coatings were studied to evaluate the surface protection behavior of zirconium alloy cladding under operation conditions of a pressurized water reactor. The results showed that all the coatings were composite structures with amorphous and bcc-structured nanocrystals. With the increase of Al content, both the elastic modulus and hardness decreased first and then increased. The hydrophobicity of the coatings was enhanced compared with that of the substrate. The 10.2 at.% Al AlNbTiZr coating had the best corrosion resistance and the minimum oxygen penetration depth, which originated from the formation of a denser oxide layer consisting of Nb2Zr6O17 and ZrO2. This study provides an improved idea for the design and development of Al-containing MEA coating materials for accident tolerant fuel.
The alloy element Nb plays an important role in improving the performance of zirconium alloys in nuclear reactors. The effect mechanism of Nb doping on mechanical and thermodynamic properties was investigated using experimental and theoretical methods. The results of this study showed us that Nb doping refines grains and enhances hardness. The hardness increases from 2.67 GPa of pure Zr to 2.99 GPa of Zr1.5Nb. Depending on the first-principles calculations, the hardness decreases with the increase in the Nb concentration in the Zr matrix, namely from 2.45 Gpa of pure Zr to 1.78 GPa of Zr1.5Nb. If the first-principles calculations indicate that the hardness decreases with the increase in the Nb concentration in the Zr matrix, grain refinement or defects could play a major role in the increase in hardness. Furthermore, regarding the effect of Nb doping on thermal expansion coefficients, the increase in Nb content causes the thermal expansion coefficients to decrease, which might stem from the strong binding energy between Nb and Zr atoms. The thermal conductivities of three samples show similar changing trends, indicating that thermal conductivity begins to decrease at room temperature and reaches a minimum value of around 400 °C. The thermal conductivity of pure zirconium samples is consistently higher, is more obvious than that of Nb-doped samples in the test range, and decreases with an increase in the doping concentration. The possible reasons for this might stem from the distortion of the Zr matrix due to Nb substitution doping and grain refinement, both of which cause phonon propagation scattering and thus hinder the propagation of phonons. The results obtained herein may be useful for the development of advanced nuclear fuels and waste forms that utilize zirconium in applications beyond their current usage.
Zirconium (Zr) alloy is a promising fuel cladding material used widely in nuclear reactors. Usually, it is in service for a long time under the effects of neutron radiation with high temperature and high pressure, which results in thermomechanical coupling behavior during the service process. Focusing on the UO2/Zr fuel elements, the macroscopic thermomechanical coupling responses of pure Zr, Zr-Sn, and Zr-Nb binary system alloys, as well as Zr-Sn-Nb ternary system alloy as cladding materials, were studied under neutron irradiation. As a heat source, the thermal conductivity and thermal expansion coefficient models of the UO2 core were established, and an irradiation growth model of a pure Zr and Zr alloy multisystem was built. Based on the user material subroutine (UMAT) with ABAQUS, the current theoretical model was implemented into the finite element framework, and the consequent thermomechanical coupling behavior under irradiation was calculated. The distribution of temperature, the stress field of the fuel cladding, and their evolution over time were analyzed. It was found that the stress and displacement of the cladding were sensitive to alloying elements due to irradiated growth.